Twvpom



cation H. 105,677, Class 12 o,

Patented Apr. 7, .1931

UNITED! STATES PATENT LEoPoLn RUzIcKA, OF DE BILT,

' ANONYME M. NAEF & co., or

LAND

NEAR'UTREGHZIQ, NETHERLANDS, ass anon 'ro SOCIETE GENEVM-SWITZERLAND, ACORPORATION or swrrznn- PROCESS r03 THEPBEPAR-ATION or THE. MONOGYCLIC'nacronns HAVING FOURTEEN i T0. EIGHTEENYRIIIG MEMBERS no Drawing,Application filed. July 16,1928,

Closed; chain lactones: having, more than seven ring members have. nothitherto been obtainable in the pure state: M. Kerschbaum has howeverstated in the Berichte der deut- 4 5 schen Chemischen Gesellschaft,1927, volume 60, pages 902 and tollowing,that in native substances alactone is present having;16' and 17 'ringmembers. It is also stated inthe'speciiication of German patent appl published the 25th-May 1927,that synthetic lactones are produced having 16 and 17 ring members,-which are formed by heating with silver oXid of brominated'fatty acidsin which the atom of bromine and the carboXyl group are at the opposite,ends of the chain. 'All these lactones-are described as beingliquidswhlch do: not possess clearly defined boiling points the yields of theseproducts ln' the syntheti- 20'c'al process are sosmall, that apreparation of the products in the pure state has apparently that nownot been possible.-

I have however found that it is possible to obtain such lactones-in thechemically pure stateandin a considerable. yield byheating carbocyclicketones having a large/number of ring members suchas those descrlbed inthe United States Patent 1,673,093 and the United States patentapplications Serial No.

.149534- to No, 149,544 now Patents Nos.

1,702,842 to 1,702,852 respectively, issued February 19, 1929, withmonopersulphuric acid ata temperature of about 30 to I60degrees-centigrade.

' 5 l I thus did obtain from cyclotridecan'one the Y12.-oXy-dodecane-l-carboxylic lactone oi acidjfrom cyclotetradecanonethelactone' of 13-oxy-tridecane 1-carboxylic acid; from,cyclo-pentadecanone (exaltone) the lactone of14-oXy-tetradecane-l-carboxylic acid (exaltolid) from cyclo-hexadecanonethe lactone of 15-0Xy-pentadecane-l-carboxylic acid and iroincyclo-heptadecanone (dihydrozibetone) the lactone of 16-oXy-heXadecan-1-5 carboxylic acid. Allthese lactones are solid at a temperature above 25degrees centigrade and possess clearly defined boiling ,points, 1

In a similar manner the corresponding lactones can be obtained fromalkylated ketones 1 described in: the

U. .S'. Patents 1,673,093,

page. 862.

Serial No. 293,310, and in switzerland'luly 27, 1927.

1,7 02,842 to 1,702,852 inclusively; for instance. from2-methyl-cyclopenta-decane-lone (lqnethyhexaltone) a mixture of lactonesof the 14-oXy-14-methyl-tetradecane-1 carboxylic acid and the14-oxy-1-methyl-tetradecane-l-carboxylic acid and from 3- methylcyclopentadecan-e-1-one (muscone) a mixture of lactones of the14-oXy-13-methyltetrade'cane-1-carboxylic acidand 14-oxy-2-methyl-tetradecane-l-carboxylic acid.

It was however already known to be possible to obtain. lactoneshaving'respectively7 or 8 rmgmembers by treating ketones having 6 orTringmembers with monopersulphuric' acid, as per Baeyer & Villiger,Berichte der deutschen Chemis-chen Gesellschaft, 1899, volume 32, page3625 and 1900, volume 33, There appeared however that only such ketonesgive a good yield of lactones, which possess beside the ketone groupsubstituents such as the isopropyl group and themethyl group. However,ketones which ,besides the keto-group do not possess any substituent didgive either no lactone at all oronly a small amount thereof. But thenone has to work below 20 degrees centigrade,

as at a higher temperatureonly the splitting product of the lactone, theoXy-acid, is formed. It could therefore not be expected thatketoneshaving a larger number of ring members might give at a highertemperature a yield of more than 50 per cent of pure lactone, even iftheypossess lateral chains approaching the keto-group. The stability of'these' lactones against: warm monopersulphuric acid is so much moreremarkable as a smallstability of the'same against hydrolizing agentswould rather be expected from the known facility to. form lactones 1having more than "sevenjring members.

When onthe contrary, the inonopersulphuric acid is allowed to act uponthe higher membered ketones under the conditions indicated by v.Baeyer&'Villiger, there is obtained onlyia small quantity of thelactone, and in v its place the peroxide ofthe ketone is formed.

When my working conditions are ,maintained the production of theseperoxides is avoided.

The constitution of the prepared unmethylated lactones was proved bysplitting the same by means of boiling potash lye to the correspondingoxyacids which when oxidized'with chromic acid are'transformed intodicarboxylic acids having the same number of carbon atoms.

f The herein described lactones have an odorresembling that of muslncivet or that of amber and may be employed in place of such perfumes oras raw materials for the preparation of similar products.

The preparation of lactones having 14 to 18 ring members represents initself an important technical progress, as it is very important for theuse of a substance as a perfume to remove from the same any impuritieswhich may influence the odor thereof.

Example 1 27 grams cyclo-pentadecanone (exaltone) are dissolved in gr.petroleum benzine and added with a filtered solution of 160 gr.persulphate of potassium in 400 gr. concentrated sulphuric acid and 74:gr. water, this addition being made so rapidly that the temperature ofthe mixture remains about degrees centigrade. A too great riseoftemperature may be avoided by an exterior cooling with ice. Afterstanding'during several hours the mixture is poured on ice and the layeroi benzine is separated. By shaking the mixture with a solution of soda,acid products are extracted. By treating the neutral portion with a 0solution of semicarbazide the remaining small quantities of unchangedcyclo-pentadecanone which are contained therein are transformed into thesemicarbazone. The easily soluble lactone of the ll-oxy-tetradecane-l-carboxylic acid may then be extracted by means ofpetroleum spirit This lactone boils at 176 degrees centigrade under 15mm. pressure, solidifies quickly into needles melting at 31 to 32degrees centigrade and presents the following characteristics:

D *=0.944l7, n lailof).

D means the density measured at a temperature of 83 degrees Centigradeand relates to water of 4 degrees centigrade;

02 or N means refractive index of the D-line of the spectrum determinedat a temperature of 33' degrees centigrade.

Example 2 grees centigrade and presents the following characteristics=O.959O n,', =1.4649.

Example 3 Cyclo-tetradecanone is treated in the manner described inExample 1. ,After the treatment of the neutral product of reaction witha solution of semicarbazide the lactone of l3-oxy-tridecane-l-carboxylicacid is extracted by means of petroleum spirit. It boils at 165 degreesCentigrade under 15 mm. pressure, melts at 29 to 30 degrees centigradeand presents the following characteristics:

D =0.9528; "n =1/l662. Example 4 Cyclo-hexadecanone is treated in themanner described in Example 1. After the treatment of the neutralproduct of reaction witha solution of semicarbazid the lactone of15-oxy-pentadecane-l-carboxylic acid is extracted by means of petroleumspirit. It boils at 188 degrees centigrade under 15 mm. pressure, meltsat 35 to 36 degrees centigrade and presents the followingcharacteristics:

Example 5 Cyclo-heptadecanone (dihydro-zibetone) is treated in themanner described in EX- ample 1. After the treatment ofthe neutralreaction product with a solution of semicarbazide the lactone of16-oXy-hexadecane-1- carboxylic acid is extracted by means of petroleumspirit; it boils at 19% degrees centigrade under 15 mm. pressure, meltsat 11 to 42 degrees centigrade and presents the followingcharacteristics Dfi =O.9326; 111, 1.4669. Example 6 D =0.93O1; n=1.4611.

Example 7 3 methyl-cyclopentadecane-1-on (muscone) is treated in themanner described in Example 1. After the treatment of the neutralreaction product with a solution of semicarbazide the mixture of thelactencs of the 14-oXy-13-methyl-tetradecane-l-carboxylic acid and14-oxy-2 methyl-tetradecane-l-carboxylic acid is extracted by means ofpetroleum spirit. The mixture of lactones boils at 180 degreescentigrade at 15 mm. pressure and presents the following characteristicsv WVith respect to the number of ring members mentioned in the claims 1and 2 the following explanation is given:

By 14 to 18 ring members applicant means that besides the 13 to 17carbon atoms there is furthermore one oxygen atom which by theconversion of the ketones into the lactones is inserted as ring member.That means in a general manner: 4

The lactone obtained from a ketone possesses one ring member more thanthe ketone, this ring member being an oxygen atom according to thefollowing formula:

1. A process for the preparation of the monocyclic lactones having 14 to18 ring members, consisting in heating monocyolic ketones having 13 to17 ring members with persulphuric acid. 7 i

2. A process for the preparation of the monocyclic lactones having 14 to18 ring members, consisting in heating monocyclic ketones having 13 to17 ring members with persulphuri'c acid at a temperature of about 30 to60 degrees Centigrade.

3. A process for thepreparation of the lactone from14-oxy-tetradecane-l-carboxylic acid, consisting in heatingcyclo-pentadecanone with persulphuric acid.

4. A process for the preparationof the lactone from14-oxy-tetradecane-1-carboxylic acid, consisting in dissolving.cyclo-pentadecanone in petroleum benzine. adding a solution ofpersulphate of. potassium' in sul phuric acid and water, maintaining thetemperature atabout 50 degrees centigrade, after several hours standing,pouring the mixture on ice, separatingthe layer of ben zine eX- tractingthe acid products by means of a solution of soda, treating the neutralreaction product with a solution of semicarbazide, extracting thelactone of 14-oXy-tetradecane-1- carboxylic acid by means of petroleumspirit. 5. The lactone from 14-oxy-tetradecane-1- carboxylic acidboiling at 176 degrees centigrade under 15 mm. pressure, solidifyinginto needles melting at 31-32 degrees centigrade and presenting thefollowing characteristics: D 0.9447; m 1.4669.

whereof I affix my signature.

' In testimony LEOPOLD RUZICKA.

